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As minerals, which are essential to industrial economies, are presently not in short supply,
nor do they seem to be for the next several generations, mining and mineral processing can no
longer be presumed to be the best of all possible uses for land; it must compete with compelling
demands for alternative uses. Environmental protection and rehabilitation are fast becoming
high priorities throughout the world, no longer confined to industrialized countries.
Environmental regulations in the developed countries are one of the main reasons for the
departure of metal mining companies to less developed nations in the last few decades. Low
labor costs, exploration potential, and lax or no existing environmental policies, reinforced this
process (Hodges, 1995). While industrialized countries started to formulate environmental
reports and to implement environmental framework laws in the 1970s (e.g., USA, Central
Europe, Japan), developing countries started this process only recently in the 1990s (e.g., Chile,
Peru, Korea, Nigeria), as reported in Jnicke and Weidner (1997). A main task for the future will
be to build a body of local experts in these countries, which will be able to implement the
environmental laws. Increasing world population together with economic growth in developing
countries will increase the demand for minerals in the near future and the associated
environmental assessment.
Once the exploration of an ore body is successful, exploitation begins. The extraction of
the ore can take place in an open pit or underground. The ore is then transported to stockpiles or
directly to the milling process, where crushing and grinding decrease the grain size for the
benefaction process. The ore grinding must be optimized with respect to the leaching, roastleaching, or possible benefaction circuits as tabling, flotation, high intensity magnetic
separation, heavy media, and others. Liberation of the mineral by the process is governed by the
grain size and the mineral complexity of the ore (e.g., Ritcey, 1989).
Flotation circuits are systems of cells and auxiliary equipment arranged to yield optimal
results from an ore in creating a concentrate following grinding and reagent treatment (Fig. 1).
Froth flotation involves the aggregation of air bubbles and mineral particles in an aqueous
medium with subsequent levitation of the aggregates to the surface and transfer to a froth phase.
Whether or not bubble attachment and aggregation occur is determined by the degree to which a
particles surface is wetted by water. When a solid surface shows little affinity for water, the
surface is said to be hydrophobic, and an air bubble will attach to the surface. Coal and
molybdenite are the most important hydrophobic minerals. For sulfides except molybdenite, and
possibly stibnite, as well as non-sulfide minerals, the surface condition required for flotation is
obtained by specific reagents called collectors. Furthermore, complex ores require a complex
combination of conditioning, collecting, and depressing necessary for optimal mineral extraction
(Weiss, 1985). After the extraction of the economically interesting minerals by flotation, the
residual material (in copper mines typically 95-99% of the treated material) is transported in the
form of a suspension to tailings impoundments for final deposition. In practice the recovery of
sulfide minerals is less than 100%, and pyrite flotation is generally suppressed by lime addition,
so the tailings resulting from sulfide ores contain certain percentage of sulfides, mostly pyrite.
crushing
milling
flotation
tailings impoundment
tailings 80-99%
concentrate1-20%
smelter
Fig. 1: The ore flow-path from the mine, through crushing and milling, to flotation. The concentrate is refined in
the smelter, while the main part of the treated material will be deposited on the tailings impoundments. Tailings
and concentrate proportions may differ from the given percentages.
2.1
The most economic and most commonly used tailings deposition technique is wet
deposition nearby the mine site. In this technique a water-sediment slurry is pumped in nearby
topographic depressions, lakes or drainage basins (Robertson, 1994). Other techniques are a
semi-dry subaerial method, thickened discharge, and deep-water disposal (Ritcey, 1989).
In countries with pronounced topography (e.g., Chile), most of the tailings impoundments
are designed as valley dam impoundments. This type of design is provided by placing an
embankment across the valley at the head end of drainage. The most common dam construction
methods are the downstream and the upstream methods (Robertson 1984 and 1994). In the wet
deposition method, the tailings slurry is thickened to 35-40% solids and discharged by either
point or line discharge. Often a discharge point is moved periodically. As a result of a periodical
move of the discharge point and gravimetrical grain size separation occurring in the tailings, a
general trend of coarser to finer grain size from the tailings discharge point to the pond can be
observed (Fig. 2). Additionally, inhomogeneous layering of fine sand with silt and clay horizons
makes the hydrological situation in the tailings material very complex. In general, it must be
4
assumed that the coarser horizons are responsible for water permeability, and that they are
connected aquifers. This should be taken into account in sampling and the calculation of
permeability coefficients. As the horizons have thickness in the range of centimeters to
decimeters, frequently, bulk samples lead to too low permeability coefficients.
In case of Chile, the combination of valley dam impoundments with high potential energy,
the extremely high seismic activity, and the fact that this country is very rich in mining
resources makes the stability of the tailings dam construction the largest apparent problem. In
addition, as the tailings material is generally fine-grain sized material, it retains well moisture
also in arid climates, and the process of liquefaction during seismic activity is a very important
issue (Byrne, 1991 and 1997). In contrast, the geochemical instability of tailings and waste rocks
in general is still not in the focus of interest and the present work is devoted to this aspect.
discharge point
clay
silt
fine
sand
discharge point
clay
silt
starter dam
fine
sand
starter dam
Fig. 2: Downstream (A) and upstream (B) deposition technique of tailings dam construction and the resulting
grain-size separation.
3
3.1
pH = -log{H + }
low pH = high {H + } = acid
p = -log {e - }
low p = high {e - } = reducing
Eh = Redox Potential (volt) = 0.059 x p
Alkalinity (Acid Neutralizing Capacity)
Total Alkalinity = [HCO 3 - ] + 2[CO 3 2 -] + [OH - ] - [H + ]
3.2
Terminology
For the description of the tailings mineralogy the classification proposed by Jambor (1994)
is used. The term primary is used to designate the complete ore mineralogy, i.e. hypogene
and supergene. Secondary minerals are minerals formed within the tailings impoundment as
the products of weathering processes. Tertiary minerals form after the sample has been
removed from the tailings environment.
3.3
The problem of sulfide oxidation (mainly pyrite oxidation) and the associated acid mine
drainage (AMD), or more generally acid rock drainage (ARD), as well as the solution and
precipitation processes of metals and minerals, has been a major focus of investigation over the
last 40 years (Sato, 1960; Bryner et al., 1967; Nordstrom, 1977 and 1982; Nordstrom et al.,
1979; Ritcey, 1989; Jambor and Blowes, 1994; Alpers and Blowes, 1994; Morin and Hutt, 1997;
Jambor and Blowes, 1998; Nordstrom and Alpers, 1999). There has been less interest in the
mineralogical and geochemical interactions taking place within the tailings itself (Jambor,
1994), yet this is an essential aspect to understand the parameters controlling acid mine drainage
formation and to develop effective prevention methods. The primary mineralogical composition
has possibly a strong, but at the moment poorly understood, influence on the oxidation
processes. This has been best illustrated by Rimstidt et al. (1994) showing that reaction rates
display significant differences depending on the sulfides being oxidized by Fe(III). Kinetic-type
weathering experiments indicate the importance of trace element composition in the stability of
individual sulfides. Where different sulfides are in contact with each other, electrochemical
processes are likely to occur and influence the reactivity of sulfides (Kwong, 1993).
Most mining operations are surrounded by piles of impoundments containing pulverized
material or waste from the benefaction process, which are known as tailings, stockpiles. Waste
rock dumps contain generally material with low ore grade, which is mined but not milled. These
materials commonly contain large concentrations of sulfide minerals, which may undergo
oxidation, producing a major source of metal and acid contamination. The complex
microbiological, hydrological, mineralogical, and geochemical post-depositional processes and
their coupled interaction in mine waste environment are not yet completely understood. In the
following section the focus is on the acid producing sulfide minerals, other acid producing
processes, and the acid neutralizing processes, as well as on the controlling factors for element
mobility.
3.3.1
and (3) hydrolysis and precipitation of ferric complexes and minerals (equation 4). The kinetics
of each reaction are different and depend on the conditions prevailing in the tailings.
FeS2 + 7/2O2 + H2O Fe2+ + 2SO42- + 2H+
Fe2+ + 1/4O2 + H+
Fe3+ + 1/2H2O
(1)
(2)
FeS2 + 14 Fe + 8H2O
2+
+
215 Fe + 2SO4 + 16H
(3)
Equation (1) describes the initial step of pyrite oxidation in the presence of atmospheric
oxygen. Once ferric iron is produced by oxidation of ferrous iron, oxidation which may be,
especially at low pH conditions, strongly accelerated by microbiological activity (equation 2),
ferric iron will be the primary oxidant (equation 3) of pyrite (Nordstrom, 1979; Moses et al.,
1987; Ehrlich, 1996). Under abiotic conditions the rate of oxidation of pyrite by ferric iron is
controlled by the rate of oxidation of ferrous iron, which decreases rapidly with decreasing pH.
Below about pH 3 the oxidation of pyrite by ferric iron is about ten to a hundred times faster
than by oxygen (Ritchie, 1994).
It has been known for nearly 30 years that microorganisms like Acidithiobacillus
ferrooxidans obtain energy by oxidizing Fe2+ to Fe3+ from sulfides by catalyzing this reaction
(Bryner et al., 1967) and this may increase the rate of reaction (2) up to the factor 105 over
abiotic oxidation (Singer and Stumm, 1970). More recent results suggest that a complex
microorganism fauna is responsible for sulfide oxidation (Norris, 1989; Rossi, 1990; Gould et
al., 1994; Ehrlich, 1996; Nordstrom & Southam, 1997; Blowes et al., 1998). Nordstrom and
Southam (1997) states that the initiating step of pyrite oxidation does not require an elaborated
sequence of different geochemical reactions that dominate at different pH ranges.
Acidithiobacillus spp. form nanoenvironments (nanometer scale) to grow on sulfide mineral
surfaces. These nanoenvironments can develop thin layers of acidic water that do not affect the
bulk pH of the water chemistry. With progressive oxidation, the nanoenvironments may change
to microenvironments (micrometer scale). Evidence of acidic microenvironments in the
presence of near neutral pH for the bulk water can be inferred from the presence of jarosite (this
mineral forms only under pH < 3) in certain soil horizons where the current water pH is neutral
(Carson et al., 1982). Barker et al. (1998) observed microbial colonization of biotite and
measured pH in microenvironments in the surroundings of living microcolonies. The solution
pH decreased from near neutral at the mineral surface to 3-4 around microcolonies living within
confined spaces at interior colonized cleavage planes.
When the acid mine water, rich in ferric iron, reaches the surface it will fully oxidize,
hydrolyze and may precipitate to ferrihydrite (fh), schwertmannite (sh), goethite (gt), or jarosite
(jt) depending on pH-Eh conditions (Fig. 4), and availability of key elements such as potassium
and sulfur (Nordstrom et al., 1979; Bigham et al., 1996). Jarosite, schwertmannite and
ferrihydrite are meta-stable with respect to goethite (Bigham et al., 1996).
The hydrolysis and precipitation of iron hydroxides (and to a lesser degree, jarosite) will
produce most of the acid in this process. If pH is less than about 3.5, Fe(OH)3 is not stable and
Fe3+ remains in solution:
Fe3+ + 3 H2O
+ 3H+
Fe(OH)3(s)
(4)
Note that the net reaction of complete oxidation of pyrite, hydrolysis of Fe3+ and precipitation of
iron hydroxide (sum of reactions 1, 2 and 4) produces 4H+ per mol of pyrite (in case of Fe(OH) 3
formation, see equation 5, i.e., pyrite oxidation is the most efficient producer of acid of the
common sulfide minerals (net reaction 5; Table 2). Nevertheless, it is important to be aware that
the hydrolysis of Fe(OH) 3 is the main acid producer (3/4 of H+ per mol pyrite).
15
7
FeS2 + /4O2 + /2H2O
-9.21 (Jt)
-12.51 (Jt)
20
4.5 (Fh)
pe = Eh (mv)/59.2
16
Jt
5.0 (Fh)
O2
Sh
12
8
(5)
H 2O
Fh
dissolved
species
Gt
Py
-4
H 2O
-8
H2
-12
2
pH
Fig. 3: pe-pH diagram for Fe-S-K-O-H system at 25C where pe = Eh(mV)/59.2; total log activities of Fe2+ = 3.47; Fe3+ = 3.36 or 2.27; SO42- = -2.32; K+ = -3.78; log Kso values for solid phases for Gt = goethite, Jt = Kjarosite, Fh = ferrihydrite, Sh = schwertmannite are 1.40,
equations are: Gt (pe = 19.22-2.6 pH); Jt (pe = 16.21-2 pH); Fh (pe = 21.50-3 pH); Sh (pe 19.22-2.6 pH), and Py
(pe = 5.39-1.14 pH). Fields of metastability are shown by dashed lines. Single-hatched areas demonstrate
expansion of K-jarosite and ferrihydrite fields if lower Ksos are selected. Mean composition of the schwertmannites
used for the development of this pe-pH diagram was Fe8O8(OH)4.8(SO4)1.6. From Bigham et al. (1996).
Evangelou and Zhang (1995) reported increased oxidation rates of pyrite by addition of
HCO3 due to the formation of pyrite surface Fe(II)-CO3 complexes. This means that the
frequent applied limestone treatment for mine waste management must be discussed critically,
because if it is able to neutralize the acid produced, it can also increase the kinetic of pyrite
oxidation.
Marcasite, the orthorhombic dimorph of pyrite, may also abundantly occur as a primary
mineral in sulfidic tailings, mainly from sediment-hosted base metal deposits and as primary
alteration product of pyrrhotite. Marcasite has the same formula as pyrite and leads to the same
amount of acid production via oxidation. Direct observation (e.g. the Zn-Pb deposit of Reocn,
Spain) suggest that its oxidation kinetics should be faster than that of pyrite, perhaps as a result
of its typical twinned morphology and finer grain size, which offers more surface to oxidation
than pyrite. In the tailings studied in the present work, marcasite was not identified. Additional,
Jambor (1994) reports the presence of marcasite as a secondary alteration product of pyrrhotite
in zonal patterns in oxidizing mine tailings.
-
3.3.1.2 Pyrrhotite(Fe(1-x)S)
Wastes from sulfide ores often contain pyrrhotite associated with pyrite. The general
formula of pyrrhotite is Fe(1-x)S, where x can vary from 0.125 (Fe7S8) to 0.0 (FeS, troilite). The
oxidation rates and weathering products of pyrite are well known, but only a few investigations
have focused the oxidation of pyrrhotite. Nicholson and Scharer (1994) propose for the
oxidation of pyrrhotite the following equation:
Fe(1-x)S + (2-x/2)O2 +xH2O (1-x)Fe2+ + SO42- +2xH+
(6)
in which the stoichiometry of the pyrrhotite affects the relative production of acid. At one
extreme, if x = 0 and the formula is FeS, no H+ will be produced in the oxidation reaction; at the
other extreme, the maximum amount of acid will be produced by the iron-deficient Fe7S8 phase.
The main part of acid is produced by the oxidation of pyrite (equation 1) and the subsequent
hydrolysis of ferric hydroxides (equation 4). In conclusion, the role of pyrrhotite in the
acidifying process is similar to that of pyrite, but it is very important at early weathering stages
because its oxidation rate is 20 to 100 times higher than that of pyrite in atmospheric
concentrations of O2 and at 22C (Nicholson and Scharer, 1994).
The oxidation of pyrrhotite can also involve the formation of elemental sulfur (Ahonen
and Tuovinen, 1994), marcasite (Jambor, 1994), or the formation of pyrite (Burns and Fischer,
1990). They are acid-consuming reactions.
(7)
without acid production (Walder and Schuster, 1998). Nevertheless, the combination of ferrous
iron oxidation and ferrihydrate hydrolysis will be again the main acid producing process.
2CuFeS2 + 17/2O2 +5 H2O 2Cu2++ 2Fe(OH)3 + 4SO42- + 4H+
(8)
Chalcopyrite, together with molybdenite, is known as one of the most resistant sulfides to
oxidation (Plumlee, 1999). Rimstidt et al. (1994) reported that the oxidation rate of chalcopyrite
increases with increasing ferric iron concentration, but with an oxidation rate of 1-2 orders of
magnitude less than pyrite.
(9)
Combined with ferrous iron oxidation and ferrihydrate precipitation, the overall arsenopyrite
oxidation reaction can be written as follow:
FeAsS + 7/2O2 + 6H2O Fe(OH)3 + SO42- + H2AsO4- + 3H+
(10)
If ferric iron is the oxidant, the oxidation rate of arsenopyrite is similar to the oxidation rate of
pyrite. If it is oxygen, the oxidation rate of arsenopyrite is somewhat lower than that of pyrite
(Mok and Wai, 1994).
10
Table 1: Hydrogen ions per mole produced by oxidation via O2 of some frequent minerals in mine tailings (Walder
and Schuster, 1998; Plumlee, 1999) and some laboratory reaction rate data from Rimstidt et al. (1994). However,
Jambor (1994) suggested the relative resistance of sulfide in oxidizing tailings environment to follow the increasing
order pyrrhotite sphalerite-galena pyrite-arsenopyrite chalcopyrite magnetite:
Mole H+/Mole
Mineral
Relative wt %
H+/Mole mineral
Reaction with
Fe(III)1)
Pyrite
0.03
2.7 x 10-7
Marcasite
0.03
1.5 x 10-7
Arsenopyrite
0.018
1.7 x 10-6
Chalcopyrite
0.011
9.6 x 10-9
2-0
0.022
Mineral
Pyrrhotite
Enargite
1
0.002
1) m
-3
-2 -1
Fe3+ = 10 and pH = 2.5 at 25C; mol m s ; - = not studied by Rimstidt et al. (1994)
3.3.2
(11)
(12)
Secondary anglesite coating on galena may increase the apparent resistance because anglesite
has a low solubility and protects the sulfides from direct contact with oxidizing reagents
(Jambor and Blowes, 1998). The oxidation process does not give rise to acidity when oxidation
from O2 is considered, as it is also in case of the Cu-sulfide minerals covellite, chalcocite,
digenite and djurleite which may occur as hypogene, supergene, as well as secondary phases
(Dold, 1999). In the presence of Fe3+, the oxidation of MeS (where Me = divalent metal)
produces acidity according to reaction schemes where part of the oxidation capacity of the
system is derived from Fe3+ as, e.g.
11
(13)
Plumlee (1999) pointed out that the oxidation of sulfide minerals by aqueous ferric iron
generates significantly greater quantities of acid than the oxidation by oxygen (e.g., equation 3
and 13). This is correct in the case that ferric iron is added to the system (e.g., in form of
primary ferric minerals or seepage of ferric iron containing solutions). However, if we consider
that the ferric iron is produced by the oxidation from ferrous iron in the system (e.g.,
microbiologically catalyzed pyrite oxidation), for every mole of ferric iron produced one mole
of protons is consumed (equation 2). This leads to the same overall produced quantity of two
protons per mole pyrite oxidized as in case of pyrite oxidation via O2 (compare equations 1, 2,
and 3). Additionally, in case of oxidation via ferric iron no acidity can be produced via the
hydrolysis of the ferric phases, the main acid producing process in sulfide oxidation (see
equation 4). Thus, the sulfide oxidation by ferric iron has faster kinetics and is able to oxidize
sulfide minerals in the absence of oxygen, but it does not produce more acid as the oxidation via
oxygen when the ferric iron is produced in the system.
Table 1 shows a summary of the hydrogen ions produced by some common sulfide
minerals by the oxidation via O2. There are important differences and therefore exact knowledge
of the sulfide minerals contained in waste rocks or tailings is crucial for adequate acid-base
accounting (ABA).
3.3.3
As explained in 2.4.1, the acid production processes can be split into two parts. The first is
the oxidation of sulfide minerals by oxygen and ferric iron. The second is the hydrolysis of
mainly Fe(III) and subsequent precipitation of ferric oxyhydroxides or oxyhydroxide sulfates.
The process of hydrolysis of Fe(III) has been reviewed by Sylva (1972), Flynn (1984),
Schneider and Schwyn (1987), Stumm and Morgan (1996), and Cornell and Schwertmann
(1996). Metal ions undergo hydrolysis because coordinated water is a stronger acid than free
water. This results from the effect that the metal-oxygen bond weakens the O-H bonds in a way
that in aqueous systems the free water molecules behave as proton acceptors. So the hydrolysis
of metal ions is the result of the deprotonation of the coordinated water molecules (Sylva, 1972).
The hydrolysis, i.e. deprotonation, starts with the hexa-aquo ion (Fe(III) is hydrated by 6
water molecules), except at very low pH, where Fe3+ is stable. Initially, low molecular weight
species such as Fe(OH)2+ and Fe(OH)21+ form rapidly. The following dissolved species will be
stable depending on pH (see also Fig. 6 and Table 3): Fe3+, Fe(OH)2+, Fe(OH)21+ , Fe(OH)3 (aq),
Fe(OH)4-, Fe2(OH)24+, and Fe3(OH)45+ (Stumm and Morgan, 1996). By aging increasingly
complex polymers, Fe(III) oxides, oxyhydroxides, or oxyhydroxide sulfates are formed (Fig. 3).
12
Table 2: Hydrolysis reactions of Fe(III) species and the associated protons produced (from Stumm and Morgan,
1996).
Species
Equation
Fe3+
H+
log K (I = 3 M)
1
1
1
1
1
2
3
0
-1
-2
-3
-4
-2
-4
0
-3.05
-6.31
-13.8
-22.7
-2.91
-5.77
3+
Fe
Fe(OH)2+
Fe(OH)2+
Fe(OH)3 (aq)
Fe(OH)4Fe2(OH)24+
Fe3(OH)45+
3+
2+
Fe + H2O Fe(OH) + H
Fe3+ + 2H2O Fe(OH)2+ + 2H+
Fe3+ + 3H2O Fe(OH)3 (aq) + 3H+
Fe3+ + 4H2O Fe(OH)4- + 4H+
2Fe3+ + 2H2O Fe2(OH)24+ + 2H+
3Fe3+ + 4H2O Fe3(OH)45+ + 4H+
Depending on the secondary phases precipitated, considerably different amounts of protons are
produced (Table 3)
Table 3: Amount of protons produced by the hydrolysis of the different secondary Fe(III) phases.
Phase
Equation
moles H+/mole
Fe3+hydrolyzed
amp. Fe(OH)3(s)
ferrihydrite
goethite
hematite
schwertmannite
jarosite
3.3.4
Fe3+ + 3H2O
10 Fe3+ + 60H2O
Fe3+ + 2H2O
3+
2Fe + 3H2O
Fe(OH)3(s) + 3H+
5Fe2O3.9H2O + 30H+
FeO(OH)+ 3H+
Fe2O3 + 6H+
3
3
3
3
2.75
2.625
2
13
Transformation:
jarosite goethite:
(14)
2-
schwertmannite goethite:
schwertmannite goethite:
Neutralization Processes
The acid produced in the processes presented above may result in pH in the range of 1.5
4 in mine tailings. This acid together with Fe(III), are able to dissolve minerals and mobilize
elements in the tailings (Al et al., 1994; Dold, 1999). In their pathway, the acid produced and the
elements mobilized react with acid-neutralizing minerals such as carbonates or silicates. Acidneutralizing reactions result in an increase in the pore-water pH. This increase in pH is
frequently accompanied by precipitation of metal-bearing oxyhydroxide and oxyhydroxide
sulfate minerals that remove dissolved metals from the water migrating within the tailing pores.
These secondary minerals act in a certain pH range as buffers so that a sequence of pH buffering
reactions can be observed in the tailings environment (Blowes and Ptacek, 1994).
3.4.1
Carbonates
Dissolution of carbonates releases alkaline earth and metal cations, including Ca, Mg, Fe,
and Mn. These cations participate in the formation of secondary solids, including simple
hydroxide solids, which in some cases can later dissolve and contribute to acid neutralization.
The ability of carbonates to neutralize acid by fast reaction makes them an important part of the
mineralogical assemblage for ARD prediction and prevention.
(17)
14
(16)
This reaction will buffer at near neutral pH (6.5 - 7), while in more acidic environments the
following equation can be written:
CaCO3 + 2H+ Ca2+ + CO2 + H2O
(18)
Carbonate speciation is pH dependent (Fig. 4) and the dissolution of calcite increases the
amount of carbonate in solution, increasing therefore the neutralization potential of the solution.
It is important to mention that calcite buffers the pH to neutral values and at pH 7 HCO3- is the
dominant specie (Fig. 4). Thus, for the neutralization of 1 mol H+ 1 mol calcite is necessary as
shown in equation (17). Most acid-base accounting procedures (ABA) assume that H2CO3 is the
dominant specie. This is the case at lower pH and doubles the buffer capacity of calcite
(equation 18), what may lead to an overestimation of the neutralization potential at neutral pH.
When neutralization proceeds and pH increases, calcite may precipitate as a secondary mineral.
0
-2
log concentration
CO32-
HCO3-
H2CO3
-4
-6
-8
-10
-12
-14
10
12
14
pH
Fig. 4: Distribution of solute species in the aqueous carbonate system. Log concentration vs. pH for 10-3.5 M
solution of dissolved CO2 in closed system.
15
(19)
Combined with ferrous iron oxidation and ferrihydrate precipitation, the overall siderite
oxidation reaction is:
4FeCO3 + O2 + 10H2O 4HCO3- + 4Fe(OH)3 + 4H+
(20)
This indicates that under elevated pH, where bicarbonate is stable, the total reaction from
dissolution of siderite to the precipitation of ferrihydrate gives a net acid production of one mole
hydrogen ion per mol siderite dissolved. However, under more acidic conditions, where
carbonic acid is stable, there will be no net acid production (Walder and Schuster, 1998).
If ferrous iron is present in a solution containing bicarbonate, the formation of siderite
may occur by the following reaction:
Fe2+ + HCO3- FeCO3 + H+
(21)
This reaction buffers the pH at around 5 - 5.5. This reaction path may be an alternative to ferrous
to ferric iron oxidation and the consecutive precipitation of Fe(III)oxyhydroxides. Geochemical
studies by several authors have shown that in tailing impoundmends and AMD affected aquifers
the waters are frequently close to saturation or even oversaturated with respect to siderite (Morin
and Cherry, 1986; Blowes et al., 1991; Blowes and Ptacek, 1994).
3.4.2
Lime (Ca(OH)2)
Lime is a common agent in the flotation circuit to depress the flotation of pyrite by the
increase of the pH to 10.5.
Ca(OH)2 + 2H+ Ca2+ + 2H2O
(22)
(23)
Lime is used in hydrometallurgical processes due to its high solubility in water and fast
neutralization reaction. It may be washed out from tailings impoundments. In this case, the role
in neutralizing the acid produced in the tailings may be minor so that for pH buffering in mine
wastes (tailings and waste dumps) carbonates should be preferred.
3.4.3
16
(24)
(25)
(26)
These reactions complement an ideal neutralization sequence which starts with calcite (pH 6.5 7.5) followed by siderite (pH 5.0 - 5.5). When all carbonates are consumed the next neutralizer
is gibbsite (pH 4.0 - 4.3), followed by Fe(III)hydroxides as goethite (pH below 3.5). This leads
to a typical pH profile as shown in Fig. 6.
early stage
intermediate stage
late stage
pH
4
pH
6
pH
6
Al(OH)3
siderite
depth
siderite
calcite
Fe(OH)3
Al(OH)3
siderite
calcite
calcite
Fig. 6: Development of pH buffering zones during early, intermediate, and late stages of sulfide oxidation in
tailings impoundments (from Blowes and Ptacek, 1994).
3.4.4
Silicates
Dissolution of most aluminosilicate minerals also consumes H+ ions and contribute base
cations (Ca, Mg, Fe(II)), alkali elements (Na, K) and dissolved Si and Al to the tailing pore
water (Blowes and Ptacek, 1994). Though, dissolution of aluminosilicate minerals is slower than
of metal hydroxides and much slower than that of carbonates (Table 4). Feldspar weathering is
mainly controlled by pH, silica, Na, K, and Ca concentrations. One possible reactions path is:
K-feldspar -> kaolinite -> gibbsite
17
(27)
kaolinite
In this reaction, K and Si enter the solution, while protons are consumed. The solubility of
feldspar increases when proton activity increases or the removal of K or Si is fast, e.g. by
secondary mineral formation. Secondary kaolinite may dissolve to form gibbsite, a reaction that
does not neutralize acid:
AlSi2O5(OH)4 + 5H2O 2Al (OH)3 + 2H4SiO4
kaolinite
(28)
gibbsite
Higher pH and K concentrations can lead theoretically to sericite formation instead of kaolinite
as secondary mineral of feldspar weathering:
3KAlSiO3O8 + 12H2O + 2H+ KAl2(AlSi3O10)(OH)2 +2K+ + 6H4SiO4
K-feldspar
(29)
sericite
(30)
gibbsite
However, these reactions have to be seen as a strong simplification of the very complex clay
mineral group and their formation processes. In the case of plagioclase, the weathering path is
similar to that of K-feldspar and is accompanied by the release of sodium and/or calcium. Under
low pH conditions plagioclase will react to form kaolinite, while under higher pH smectite will
be formed (Walder and Schuster, 1998).
Nesbitt and Jambor (1998) have shown the fundamental role of mafic minerals in
neutralization of the Waite-Amulet tailings. As in the weathering of feldspar, the weathering of
felsic minerals leads to the formation of clay minerals. Muscovite, pyroxene, and amphibole
alter to chlorite. By decreasing pH, chlorite alters to sericite, kaolinite or Mg-montmorillonite.
The products of biotite alteration are hydrobiotite, a regularly interstratified biotite-vermiculite
phase, vermiculite, and kaolinite (Acker and Bricker, 1992; Malmstrm and Banwart, 1997).
Direct conversion of biotite to kaolinite has also been described (e.g., Acker and Bricker, 1992).
The alteration from biotite to vermiculite may be written as:
18
(31)
Malmstrm and Banwart (1997) studied the pH dependence of dissolution rate and
stoichiometry of biotite at 25C. They found that the release of the interlayer K is relatively fast
and becomes diffusion controlled within a few days. The release of framework ions (Mg, Al, Fe,
Si) is much slower. Strmberg and Banwart (1994) suggested that, in the absence of carbonates,
primary minerals, particularly biotite, provide the major sink for acidity in drainage from mine
waste rock (see equation 31). However, this statement has to be taken with care, as in the
neutralization via biotite also Fe(II) is liberated (equation 31) and may so produce acidity via
hydrolysis.
Table 4: Acid-neutralization capacity of minerals (in Jambor and Blowes, 1998, after Sverdrup, 1990).
Group
Typical Minerals
Relative Reactivity
(pH5)
1. Dissolving
1.0
2. Fast weathering
0.6
enstatite,
augite,
hornblende,
tremolite,
weathering
0.4
plagioclase
( A b100-Ab30) ,
kaolinite,
0.02
K-feldspar, muscovite
0.01
6. Inert
0.004
3.5
Dissolution
19
3.7.1 Complexation
Stumm and Morgan (1996) define complex formation as follows: Coordination or complex formation is
referred to as any combination of cations with molecules or anions containing free pairs of electrons
(bases). This combination can be electrostatic, covalent, or a mixture of both. The metal cation will be
called the central atom, and the anions are ligands. Two types of complex species can be distinguished:
the ion pairs and the complexes. Ions of opposite charge that approach within a critical distance
effectively form an ion pair and are no longer electrostatically effective. In contrast, most stable entities
that result from the formation of largely covalent bonds between a metal ion and an electron-donating
ligand are called complexes (Parks, 1990).
3.7.2 Stability of complex species
Chemical speciation and species refer to the actual form in which a molecule or ion is present in solution.
If a metal cation is liberated into solution it will be on the search for a partner. As a result, metal cations
will tend to form in water aquo- or hydroxo-complexes. This process is called hydrolysis and was
discussed in the example of ferric hydroxide formation. Fig. 3 illustrates the predominant complex species
of Fe(III) depending on the pH and the oxidation state of the central atom and of the solution.
Equilibrium in hydrolysis reactions is usually established fast, as the hydrolysis species are simple. The
aging of the solution and the associated formation of polynuclear complexes is a slower process and can
be seen as the intermediate state to the solid precipitate. Hence, hydrolysis species are thermodynamically
unstable or meta-stable. Complexes with monodenate ligants are usually less stable than those with
multidenate ligands. More important is the fact that the degree of complexation decreases more strongly
with dilution for monodenate complexes than for multidenate complexes (chelates).
3.7.3 Redox reactions
The stability of species depends strongly on the reduction-oxidation (redox) reaction taking place between
the ions. In a similar way that acids and bases are interpreted as proton donors and proton acceptors,
reductants and oxidants are defined as electron donors and electron acceptors. Because there are no free
electrons in nature, every oxidation is accompanied by a reduction, or in other words, an oxidant is a
substance that causes oxidation to occur while being reduced itself.
O2 + 4H+ + 4e- 2H2O reduction (32)
4Fe2+ 4Fe3+ + 4e- oxidation (33)
O2 + 4Fe2++ 4H+ 4Fe3+ + 2H2O redox reaction (34)
The combination of redox condition (expressed as Eh or pe) and pH makes it possible to predict which
species are dominant under the specific geochemical conditions. These stability fields are made visible in
the Eh-pH diagrams largely used in geochemistry (e.g., Fig. 3).
3.7.4 Sorption
Sorption is a general name for adsorption, absorption, and ion exchange. Sorption also includes surface
precipitation and element diffusion. The sorption processes take place at the mineral-water interface and
are controlled by the reactivity of surface functional groups. Surface functional groups are the surface
mineral atoms that may form chemical reactions with species in solution, forming mineral-species
complexes. Whether or not a mobilized element will be adsorbed depends on the redox conditions
resulting from specific speciation of the metal complexes and on the pH dependent reactivity of the
surface functional groups of the absorbent. Oxides, oxyhydroxides and silicates surfaces in contact with
water typically are electrically charged because of ionization of the functional groups. The magnitude and
sign of this surface charge vary with the solution pH. Adsorption and absorption processes of metal ions
on iron hydroxides, clay minerals, and calcite have been well investigated in laboratory research.
Adsorption of metal ions on Fe(III) hydroxides is a function of pH, temperature, surface area of sorbent,
dissolved metal concentrations, and reaction time. Long-term studies show that metal ions may be
incorporated by diffusion into the crystalline systems of secondary ferric hydroxides. This process, where
the adsorbate becomes incorporated in the crystal structure of the adsorbent, including the formation of
solid solution by co-precipitation or solid-state diffusion, is referred to as absorption. Adsorption can be
differentiated into two processes. First, the specific adsorption or chemosorption, where the sorption at
the mineral-water interface may involve further reactions of some ions, results in the loss of one or more
waters of hydration from the adsorbate ion and the formation of a relatively strong chemical bond
between adsorbate and adsorbent (ligand exchange). The adsorbed species is referred to as an innersphere adsorption complex. A weaker interaction may occur between the hydrated ion and the mineral
surface in which waters of hydration are retained (Fig. 7). Adsorption of this type is termed non-specific,
and the adsorbed species is referred to as an outer-sphere adsorption complex.
The resulting adsorption is a function of the species stable at each pH and the net surface charge of the
adsorbent at the relevant pH, e.g. for goethite is the zero point of charge (ZPC) at pH 8. In Fig. 8
adsorption of metal cations and oxyanions are shown with the net surface charge of the adsorbent, in this
case goethite. The underlying material of the oxidation zone in mine tailings has the function of a buffer
for the acid and metal bearing solution through sorption and neutralization processes. Once the adsorption
and acid-neutralization capacity of the underlying tailings material is exceeded, the mobilized elements
may lead to formation of highly metal-bearing acid mine drainage (AMD).
3.8 Microbiological activity
As mentioned before, microbiological activity acts as a catalyst for the oxidation of ferrous to ferric iron,
a key process of the acid rock drainage (ARD) problem. Increasing awareness about the role of
microorganism in geological processes has lead recently to a new scientific direction called
geomicrobiology. The role of microorganisms in the formation of acid mine drainage associated to
tailings impoundments and mine waste environments are increasingly a new subject of investigation.
Fig. 7 Possible sorption complexes at the mineral-water interface. M represents aqueous metal ions, and H
represents protons. The figures representing diffusion and coprecipitation show two possible modes of
Cobalt (Co) absorption in calcite
Fig. 8 Adsorption of oxyanions and bivalent cations to Fe(III)hydroxides. With decreasing pH the net surface charge
becomes positive due to proton adsorption at the surface. Elements, which are stable at acidic condition as
oxyanions become preferentially adsorbed. The adsorption of metals stable as cations increases with pH
due to the increasing negative surface charge of the adsorbent.
As mentioned earlier, Acidithiobacillus ferrooxidans has been known to play a key role in sulfide
oxidation for 40 years. These acidophilic chemolithotroph and autotroph bacteria derives cellular carbon
from atmospheric CO2 fixation via the Calvin cycle and obtains energy from the oxidation of Fe(II) or
reduced S compounds (H2S, HS-, S, S2O32-, SO3-). This microbe is also reported to be a facultative H2oxidizer and is capable of surviving under anaerobic conditions by utilizing reduced S compounds as an
electron donor and Fe(III) as an electron sink. Acidithiobacillus ferrooxidans is the longest known and
most studied organism in acid mine drainage and mine waste environments. Nevertheless, a diverse
microbial population of metal-tolerant, neutrophilic to acidophilic sulfide and sulfur-oxidizing Thiobacilli
are known so far. Leptospirilum ferrooxidans seems to be the dominant genus in some acid environments
as reported from Iron Mountain, California (Edwards et al., 1998), mine tailings (Diaby et al., 2007), or
leach piles (Rawlings & Johnson, 2007). Also heterotrophic bacteria, green algae, fungi, yeasts,
mycoplasma, and amoebae have all been reported from acid mine waters. About 37 acidophilic
heterotrophs have been isolated from acid mine drainage. The highest Acidithiobacillus ferrooxidans
population have been reported at the oxidation front, while its heterophobic counterpart Acidiphilum spp.
show higher population in the upper part of an aged oxidation zone of a mine tailings. It was shown that
in a porphyry copper tailings impoundment Leptospirillum ferrooxidans is the dominant specie at the
oxidation front and also with the highest population. Recent data show complex communities structures in
pyrite oxidation and bioleaching operation. It is nowadays recongnized that a complex ecological
interactions control the biogeochemical element cycles in acid environments like the Rio Tinto River,
Spain (Gonzalez- Toril et al., 2003). There is increased release of cations from biotite (Si, Fe, Al) and
plagioclase (Si, Al) by up to two orders of magnitude by microbial activity compared to abiotic controls.
The authors also report the formation of a low pH (3-4) microenvironment associated with microcolonies
of bacteria on biotite. These results suggest that in acid rock drainage, tailings and mine waste
environments, a complex microbial ecosystem exists, of which the controlling parameters and interactions
are poorly understood. This knowledge is not only needed to prevent acid mine drainage and to minimize
its hazardous environmental impact, but also to increase metal release in bioleaching operations for more
effective metal recovery methods, important aspects for a more sustainable mining approach.